This invention relates to pigmented silica microspheres which are useful as opacifying agents for coating compositions such as latex paints and as opacifiers and fillers for fibrous substrates such as paper.
A wide variety of porous silica particles are known in the art. The porous silica particles are commonly designed for use as catalysts or catalyst supports and less commonly for use as molding powders and insulating materials. Porous silica particles used as catalysts or catalyst supports are generally relatively large spherical particles, referred to as "beads," containing typical geltype pores having a maximum diameter of less than about 0.01.mu.. Porous silica particles of this type have been prepared by acidifying an aqueous solution of sodium silicate to form a silica gel, then agitating the gel in an oil at elevated temperatures to form silica "beads" or spherical silica particles, as described, for example, in U.S. Pat. Nos. 2,384,946 and 2,528,767. Molding powders composed of porous silica microspheres having a diameter in the range of 0.1.mu. to 50.mu. have been made by spray drying sols containing colloidal silica, as described in U.S. Pat. No. 3,301,635. The microspheres produced by this process are nonuniform aggregates of colloidal silica particles which, when compacted, have pores in the size ranges of 0.02.mu. to 5.mu.. Although the porosity of the compacted silica particles provides some opacity, the opacity is insufficient for pigmentary applications.
Hollow silica spheres having an average diameter from 100.mu. to 2500.mu., useful as insulated materials, have been made by suspending particles of alkali metal silicate and a metal oxide with a compound which liberates a gas at elevated temperatures and heating the particles to 1000.degree.-2500.degree. F. (540.degree.-1371.degree. C.). The hollow silica spheres produced by this process are generally clear and transparent, rather than opaque, because the large air cell within the hollow sphere is too large to scatter light effectively.
A method for producing reticulated inorganic microparticles useful as pigment is described in U.S. Pat. No. 3,848,059. This process comprises mixing two separate water-in-oil emulsions, each containing a separate inorganic salt to form spherical shaped microparticles of an insoluble salt having an average particle size which falls within the range of 0.1.mu. to 5.0.mu.. The degree of porosity for these spherical microparticles is insufficient for use as highly effective opacifying agents.
Highly porous inorganic microparticles having an average pore diameter of 0.03.mu. are described in U.S. Pat. No. 3,855,172. The inorganic microparticles are prepared by forming a sol of inorganic colloidal particles in a polar liquid, forming a homogeneous solution of the sol with a polymerizable organic material, and polymerizing the organic material. The organic material is burned off to form the porous microparticle. While the type of porosity which results renders these particles highly effective as catalyst supports, these particles are useless as opacifying agents.
Generally, the porous silica microparticles formed by the process of the prior art are either large porous or hollow microspheres or very dense microparticles which lack sufficient opacity for use in many applications.
This invention provides for a pigmented silica microsphere by a single emulsion technique which exhibits high opacity and combines ease of preparation with economy.